Bond Coupled Electron Transfer Reactions

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Professor Joshua Goodman of the Department of Chemistry at the University of Rochester, with the support of the Organic Dynamics Program, explores detailed mechanistic studies on different aspects of electron transfer reactions. The proposed research is centered on the concept that coupling the electron transfer processes to bond breaking and bond making events can increase the efficiency of electron transfer reactions. The research plan deals exclusively with the competition between return electron transfer (RET) and dissociative return electron transfer (DRET). The former is an energy-wasting decay process that has been widely studied in both singlet and triplet radical ion pairs. The latter is a rather specialized process that occurs only for triplet radical ion pairs under highly restrictive conditions for a limited set of substrates. Extensions of the scope of the DRET process will be of interest to specialists in the field of photoinduced electron transfer.Bond coupled electron transfer (BCET) reactions have the potential to drive chemical reactions. This project seeks to investigate several of these reactions. Professor Goodman will focus primarily on DRET reactions that involve cleavage of (1) C-C bonds in disubstituted cyclopropanes and diarylethanes, (2) Si-Si bonds in disilanes, and (3) C-halogen bonds in substituted benzylic halides. An improved understanding of RET processes in photoinduced electron transfer reactions may eventually lead to the ability to drive chemical reactions using light. For example, it may be possible one day to employ polymerizations induced by light in imaging applications. The proposed investigation on disilanes may have an impact on developing lithographic resists, nonlinear optical materials, and one-dimensional conductors.